Environmental context. Polyfluorinated substances are anthropogenic chemicals that have been widely used in several industrial and commercial applications. Analysis of human plasma samples collected from Münster in Germany revealed, since the year 2000, increasing amounts and proportion of unidentified organofluorines. The increasing trend of unidentified organofluorines in plasma samples suggests that humans are being exposed to new and unidentified fluorinated products.

Abstract. Samples of human plasma (n = 122) from two German cities (collected in 1982–2009, excluding 1994) and whole blood (n = 47) from seven Chinese cities (collected in 2004) were analysed for 52 polyfluoroalkyl/perfluoroalkyl substances (PFASs) using LC-MS/MS. Quantifiable PFASs included some newly identified and commercially available chemicals PFPAs, PFPiAs, FTSAs, PAPs and di-SAmPAP, metabolites of fluorotelomer-based products (FTCAs/FTUCAs), PFCAs, PFSAs, FASAs and FOSAAs. The blood samples were also analysed for extractable organofluorine (EOF) using total organofluorine combustion ion chromatography (TOF-CIC). Seven more PFASs (C7 and C10 PFSAs, FOSAA, MeFOSAA, EtFOSAA, C13 PFCA and 8 : 2 FTSA) were detected in the Chinese samples than had been previously reported. For the German samples, PFHpS, FOSA, MeFOSA, EtFOSA, FTSAs (6 : 2, 8 : 2), PFPAs (C6, C8) and PFPiAs (C6/C6, C6/C8, C8/C8) were additional chemicals identified that were not measured in the earlier studies. Those newly identified and commercially available PFASs were either at trace levels (pg mL–1) or not detected. A mass balance of fluorine between quantifiable PFAS and EOF in the Chinese samples indicated quantifiable PFASs accounted for 31–86 % of EOF. For the German samples, the quantifiable PFAS accounted for 52–100 % and 57–100 % of EOF in Münster and Halle samples respectively. After the year 2000, an increasing amount and proportion of unidentified organofluorine were observed in Münster samples. The increasing trend of unidentified organofluorine in plasma samples suggested humans are being exposed to new and unidentified fluorinated products.